WO2015109854A1 - 有机液态源Low-K材料金属去除剂及其制备方法和应用 - Google Patents

有机液态源Low-K材料金属去除剂及其制备方法和应用 Download PDF

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WO2015109854A1
WO2015109854A1 PCT/CN2014/085905 CN2014085905W WO2015109854A1 WO 2015109854 A1 WO2015109854 A1 WO 2015109854A1 CN 2014085905 W CN2014085905 W CN 2014085905W WO 2015109854 A1 WO2015109854 A1 WO 2015109854A1
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organic liquid
liquid source
magnetic
low
titanium dioxide
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French (fr)
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王万军
袁京
杜丽萍
黄祚刚
姜标
邱长泉
李继香
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中国科学院上海高等研究院
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28002—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their physical properties
    • B01J20/28004—Sorbent size or size distribution, e.g. particle size
    • B01J20/28007—Sorbent size or size distribution, e.g. particle size with size in the range 1-100 nanometers, e.g. nanosized particles, nanofibers, nanotubes, nanowires or the like
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
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    • B01J20/28002—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their physical properties
    • B01J20/28009—Magnetic properties
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
    • B01J20/3202—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the carrier, support or substrate used for impregnation or coating
    • B01J20/3204—Inorganic carriers, supports or substrates
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
    • B01J20/3231—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the coating or impregnating layer
    • B01J20/3234—Inorganic material layers
    • B01J20/3236—Inorganic material layers containing metal, other than zeolites, e.g. oxides, hydroxides, sulphides or salts
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/34—Regenerating or reactivating
    • B01J20/3433—Regenerating or reactivating of sorbents or filter aids other than those covered by B01J20/3408 - B01J20/3425
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/34—Regenerating or reactivating
    • B01J20/345—Regenerating or reactivating using a particular desorbing compound or mixture
    • B01J20/3475—Regenerating or reactivating using a particular desorbing compound or mixture in the liquid phase

Definitions

  • the invention belongs to the field of chemical compositions, and in particular relates to a metal remover for Low-K materials, a preparation method and application thereof.
  • organosilicon compounds such as tetramethylsilane, dimethyldimethoxysilane, octamethylcyclotetrasiloxane, and trifluoropropylcyclotrisiloxane can be used as organic materials for Low-K materials.
  • Liquid source but the organic liquid source of the Low-K material sold on the market usually contains a relatively high concentration of different metal impurities, which will significantly increase the dielectric constant value of the deposited film, the quality and dielectric of the film. The numerical value has a large influence. Therefore, prior to semiconductor fabrication, the organic liquid source of the Low-K material must be purified to remove metallic impurities.
  • an alkoxysilane or an alkoxysilane-based composition is treated with activated carbon to reduce the content of residual halogen therein and to improve the color value.
  • activated carbon has a small adsorption force for metal ions, and it is difficult to remove trace metal ions therein.
  • the adsorbent is mixed with a silicon compound, and then filtered by a filter to remove metal impurities in the silicon compound.
  • the method is simple in process and convenient in operation, but cannot remove the silicon impurity in the silicon compound and is difficult to remove trace metal impurities in the cyclopolysiloxane because of the cyclic structure of the cyclopolysiloxane and the negative ion of the Si-O bond.
  • some metal ions are easily complexed with cyclopolysiloxane, such as K + , Na + and the like.
  • the disclosure of the entire disclosure of the entire disclosure of the disclosure of the disclosure of the disclosure of the entire disclosure of the disclosure of the disclosure of the entire disclosure of the disclosure of the disclosure of the entire disclosure of A group or a chelating group imparts a function of removing a metal compound and a metal ion, and the method can remove metal impurities in a liquid having a small viscosity such as an acid, an alkali solution, an ultrapure water, an organic solvent, but it is difficult to remove the silicone.
  • Oxane is especially a trace of metallic impurities in the cyclopolysiloxane.
  • the object of the present invention is to provide an organic liquid source Low-K material metal removing agent, a preparation method thereof and an application thereof, and mainly solve the technical problem that the trace metal impurities in the organic liquid source in the prior art are difficult to remove.
  • the invention discloses an organic liquid source Low-K material metal removing agent, wherein the organic liquid source Low-K material metal removing agent is a magnetic composite hydrated titanium dioxide, and the core material of the magnetic composite hydrated titanium dioxide has a particle diameter of 10 nm to 30 ⁇ m. Fe 3 O 4 or ⁇ -Fe 2 O 3 magnetic particles, the surface of the magnetic particles being coated with hydrated titanium dioxide, the magnetic particles being covalently bonded to the hydrated titanium dioxide, wherein the magnetic composite hydration
  • the hydrated titanium dioxide in the titanium dioxide has a mass content of 40 to 65%.
  • the hydrated titanium dioxide in the magnetic composite hydrated titanium dioxide has a mass content of 46 to 63%.
  • the Low-K material metal removing agent is obtained by treating the magnetic particles treated with the surface crosslinking agent or without any treatment through the sol-gel reaction surface complex hydrated titanium oxide.
  • the organic liquid source described in the present invention refers to tetramethylsilane, dimethyldimethoxysilane, octamethylcyclotetrasiloxane, trifluoropropyl as a Low-K material in a semiconductor manufacturing process.
  • An organosilicon compound such as cyclotrisiloxane.
  • the invention also discloses a method for preparing a metal liquid source Low-K material metal remover, comprising the following steps:
  • Magnetic particles are added to an alcohol solution of butyl titanate to prepare a magnetic particle dispersion; the magnetic particles are Fe 3 O 4 or ⁇ -Fe having a particle diameter of 10 nm to 30 ⁇ m. 2 O 3 ;
  • the hydrated titanium dioxide precipitate on the surface of the magnetic particle by a sol-gel process: adding a mixed solution of an acid, an alcohol and water to the magnetic particle dispersion in the step 1) to carry out a sol-gel reaction, and solidifying after the reaction is completed Liquid separation to obtain a magnetic solid to obtain the Low-K material metal remover; wherein the acid is selected from one or more of hydrochloric acid, nitric acid, phosphoric acid or sulfuric acid; the reaction of the sol-gel process The temperature is 20 to 70 ° C; the quality of the hydrated titanium dioxide in the Low-K material metal remover is 30 to 70%;
  • the volume ratio of the magnetic particles to the butyl titanate is 1:0.5 to 1:15; and the volume ratio of the butyl titanate to the alcohol is 1:2 to 1:30.
  • the volume of the alcohol refers to the total alcohol volume used in the steps 1) and 2) of the method for preparing the organic liquid source Low-K material metal remover; the butyl titanate and the acid
  • the volume ratio is 1:0.005 to 1:0.5; the volume ratio of the butyl titanate to water is 1:0.1 to 1:2.0.
  • the mass ratio of the magnetic particles to the butyl titanate is 1:2 to 1:10.
  • the volume ratio of the butyl titanate to the alcohol is from 1:3 to 1:20.
  • the volume ratio of the butyl titanate to the acid is 1:0.02 to 1:0.3.
  • the volume ratio of the butyl titanate to water is from 1:0.2 to 1:1.0.
  • the time of the sol-gel reaction in the above step 2) is based on the complete gelation of the solution.
  • the water in the step 2) is a hydrolyzed reactant of butyl titanate, and by controlling the concentration and flow rate of the mixed solution of the acid, the alcohol and the water, the butyl titanate gels on the surface of the magnetic particle in the solution. .
  • the alcohol described in the above step is selected from alcohols commonly used in the prior art, including one or more of methanol, ethanol, propanol or butanol.
  • the magnetic particles may also be cross-linked.
  • the magnetic particles are subjected to a surface crosslinking treatment in advance, and the crosslinking treatment step is: adding a crosslinking agent to the aqueous solution of the magnetic particles for crosslinking treatment, the magnetic property
  • the mass ratio of the particles to the crosslinking agent is 1:0.1 to 3.0.
  • a crosslinking agent is added to the acid of the above step 2), and the magnetic particles are cross-linked in a mixed solution of the alcohol and the water, and the mass ratio of the magnetic particles to the crosslinking agent is 1:0.1. ⁇ 3.0.
  • the crosslinking treatment step is carried out simultaneously with the sol-gel reaction.
  • the crosslinking agent is selected from one or both of glutaraldehyde or a silane coupling agent.
  • the silane coupling agent is selected from one or more of KH570, KH560 or KH550.
  • a crosslinking agent is added to the aqueous solution of the magnetic particles under stirring.
  • a crosslinking agent is added to the aqueous solution of the magnetic particles at a temperature of from room temperature to 90 °C.
  • a crosslinking agent is added to the aqueous solution of the magnetic particles at a temperature of 50 to 80 °C.
  • the magnetic particles in the above step 1) are soaked and stirred with an anhydrous alcohol solution before use, and then subjected to solid-liquid separation, and the solid particles separated by solid-liquid separation are dried.
  • the anhydrous alcohol solution is an alcohol commonly used in the prior art, including methanol, ethanol or propanol.
  • the method for preparing an organic liquid source Low-K material metal remover further comprises subjecting the magnetic solid in the step 2) to an aged condition at 60 to 120 ° C.
  • the aging treatment described in the present invention is such that after the reaction in the step 2) is completed, the magnetic solid is further placed at 60 to 120 ° C and the reaction is continued without stirring.
  • the aging treatment time is at least 12 hours. The aging treatment is carried out without stirring, and the sol-gel reaction needs to be carried out under stirring.
  • the method for preparing a metal remover for a Low-K material further comprises performing multiple water washing and solid-liquid separation on the aged magnetic solid to remove unreacted impurities and hydrated titanium oxide not coated with magnetic particles, and finally using pH.
  • the magnetic solid is dried by washing with 2.0 to 6.0 distilled water and solid-liquid separation.
  • the invention also discloses the use of the organic liquid source Low-K material metal remover for removing metal impurities in an organic liquid source.
  • the Low-K material metal remover removes metal impurities in the organic liquid source
  • the process includes the following steps:
  • Step 1 stirring an organic liquid source and the Low-K material metal remover to form a mixture
  • step 2 a mixture of the aforementioned organic liquid source and the Low-K material metal remover is heated and vaporized, and then the fractions at different stages are collected by condensation.
  • the mass ratio of the organic liquid source to the Low-K material metal remover is from 10,000:1 to 10:1.
  • the organic liquid source and the Low-K material metal remover form a mixture in the rectification tank, which is vaporized and condensed in the rectification column.
  • the preparation method of the Low-K material metal remover is simple: it is prepared by a mild sol-gel reaction; the raw material cost is low, and the production cost is reduced; the solid-liquid separation can be realized by the external magnetic field, and the speed of solid-liquid separation can be achieved. Fast, low energy consumption.
  • the Low-K material metal remover can effectively remove trace metal impurities in the organic liquid source.
  • the organic liquid source and the Low-K material metal remover are mixed in the rectification column, and purified by rectification, so that the purity of the organic liquid source reaches 99.9% or more.
  • FIG. 1 is a schematic view showing the structure of a rectification apparatus for removing metal impurities in an organic liquid source by a Low-K material metal remover in an embodiment of the present invention.
  • the content of hydrated titanium dioxide (weight content) in the metal remover A accounted for 46% by X-ray elemental analysis and TGA water content analysis.
  • the content of hydrated titanium dioxide (weight content) in the metal remover B accounted for 53% by X-ray elemental analysis and TGA water content analysis.
  • the content of hydrated titanium dioxide (weight content) in the metal remover C accounted for 63% by X-ray elemental analysis and TGA water content analysis.
  • the content of hydrated titanium dioxide (weight content) in the metal remover D accounted for 47% by X-ray elemental analysis and TGA water content analysis.
  • the metal remover prepared in the above embodiment removes trace metal impurities in the organic liquid source, it can be carried out in a rectification column.
  • Figure 1 there is shown a schematic view of the structure of a rectification apparatus used for the removal of metal impurities in an organic liquid source by a Low-K material metal remover.
  • the rectification apparatus includes a magnetic heating agitator 11, a rectification tank 12, a rectification column 13, and a condenser 14.
  • the magnetic heating stirrer 11 is combined with the rectifying tank 12, and is adapted to stir and heat the rectified material in the rectifying tank 12.
  • the rectification tank 12 is made of quartz or stainless steel, and the openings may have two, three or four, and the size is 5L to 20L.
  • the rectification column 13 is located above the opening of the rectification vessel 12, and is made of quartz or stainless steel, having an inner diameter of 30 mm to 80 mm, a column height of 1.2 m to 2 m, and a filling height of the filler of 1.2 m to 2 m, which may be stainless steel.
  • the condenser 14 is located above the rectification column 13, wherein the condensate enters from the inlet b and exits from the outlet c.
  • the top opening v of the condenser is adapted to be connected to a vacuum machine and is adapted to be evacuated.
  • the receiving bottles 15, 16, 17 are connected to the rectification column 13 and are adapted to receive fractions of different boiling points, respectively.
  • Valves 18, 19, 110 are connected between the receiving bottles 15, 16, 17 and the rectification column 13, primarily to control the flow of different fractions into different receiving bottles.
  • the organic liquid source material is industrial grade trifluoropropylcyclotrisiloxane (purity: 98.5%), the main silicone impurity is high boiling organic siloxane, and the total metal ion content is 6.2 ppm.
  • the organic liquid source material is industrial grade octamethylcyclotetrasiloxane (purity: 98.0%), and the main silicone impurity is hexamethylcyclotrisiloxane, and the total metal ion content is 8.5 ppm.
  • the organic liquid source material is industrial grade trifluoropropylcyclotrisiloxane (purity: 98.5%), the main silicone impurity is high boiling organic siloxane, and the total metal ion content is 6.2 ppm.
  • the organic liquid source material is industrial grade octamethylcyclotetrasiloxane (purity: 98.0%), and the main silicone impurity is hexamethylcyclotrisiloxane, and the total metal ion content is 8.5 ppm.

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Abstract

一种有机液态源Low-K材料金属去除剂及其制备方法和应用，该金属去除剂为磁性复合水合二氧化钛，该磁性复合水合二氧化钛的内核物质为粒径10nm∼30μm的Fe3O4或γ-Fe2O3磁性颗粒，在磁性颗粒的表面包覆有水合二氧化钛，磁性颗粒与水合二氧化钛为共价键连接，该磁性复合水合二氧化钛中水合二氧化钛质量含量为30∼70%。

Description

有机液态源Low-K材料金属去除剂及其制备方法和应用 技术领域
本发明属于化学组合物领域，具体涉及一种Low-K材料金属去除剂及其制备方法和应用。
背景技术
随着集成电路芯片的尺寸的减小，具有低介电常数的沉积薄膜是先进的半导体制造的关键，因为它可使金属线更紧密地封装在一个芯片上而相邻层之间的电信号泄漏的风险较小。
在半导体制造工艺中，四甲基硅烷、二甲基二甲氧基硅烷，八甲基环四硅氧烷，三氟丙基环三硅氧烷等有机硅化合物可作为Low-K材料的有机液态源，但是以上市售的Low-K材料的有机液态源通常含有相当高浓度的不同的金属杂质，这些金属杂质会显著地增加沉积薄膜的介电常数值，对薄膜的质量和介电常数值影响较大。因此，在半导体制造之前，Low-K材料的有机液态源必须进行纯化以除去金属杂质。
在专利号为EP0957105 B1的欧洲专利文献中，公开了用活性炭对烷氧基硅烷或者基于烷氧基硅烷的组合物进行处理，来降低其中残留卤素的含量和改善色值。但是活性炭对其中金属离子吸附力较小，难以去除其中微量金属离子。
在专利号为200980149421.8的中国专利文献中，公开了将吸附剂与硅化合物混合，再用过滤器过滤的方法除去硅化合物中的金属杂质。该方法工艺简单，操作方便，但是无法去除硅化合物中的有机硅杂质而且较难去除环聚硅氧烷中的微量金属杂质，因为环聚硅氧烷的环状结构和Si-O键的负离子性，使部分金属离子易与环聚硅氧烷络合，如K+、Na+等。
在专利号为US007879198B2的美国专利文献中，公开了一种应用精馏塔来提纯有机硅化合物的方法及系统。该方法操作方便，但是无法完全去除有机硅化合物中的微量金属杂质。
在专利号为US20110259818A1的美国专利文献中，公开了将由环烯烃共聚物或环烯烃聚合物组成的熔喷非织造基材制成净化液体的过滤介质，通过向该非织造基材上引入离子交换基团或螯合基团赋予其去除金属化合物和金属离子的功能，该方法可以去除酸、碱溶液，超纯水，有机溶剂等粘度较小的液体中的金属杂质，但是很难去除有机硅氧烷特别是环聚硅氧烷中的微量金属杂质。
综上所述，传统技术中对于Low-K材料的有机液态源的提纯方式都难以完全的去除其中的金属杂质和有机杂质，随着集成电路工艺的进一步发展，需要一种更有效的方式提纯Low-K材料的有机液态源。
发明内容
本发明的目的在于，提供一种有机液态源Low-K材料金属去除剂及其制备方法和应用，主要解决现有技术中有机液态源中的微量金属杂质难以去除的技术问题。
本发明为解决上述技术问题所采用的技术方案如下：
本发明公开了一种有机液态源Low-K材料金属去除剂，所述有机液态源Low-K材料金属去除剂为磁性复合水合二氧化钛，所述磁性复合水合二氧化钛的内核物质为粒径10nm～30μm的Fe3O4或γ-Fe2O3磁性颗粒，在所述磁性颗粒的表面包覆有水合二氧化钛，所述磁性颗粒与所述水合二氧化钛为共价键连接，其中，所述磁性复合水合二氧化钛中水合二氧化钛质量含量为40～65％。优选地，所述磁性复合水合二氧化钛中水合二氧化钛质量含量为46～63％。
本发明中，所述的Low-K材料金属去除剂为将表面交联剂处理或未经任何处理的磁性颗粒通过溶胶-凝胶反应表面复合水合二氧化钛获得。
本发明中所述的有机液态源是指在半导体制造工艺中，作为Low-K材料的四甲基硅烷、二甲基二甲氧基硅烷，八甲基环四硅氧烷，三氟丙基环三硅氧烷等有机硅化合物。
本发明还公开了一种制备有机液态源Low-K材料金属去除剂的方法，包括如下步骤：
1)磁性颗粒分散液的制备：将磁性颗粒加入到钛酸丁酯的醇溶液中制成磁性颗粒分散液；所述的磁性颗粒为粒径为10nm～30μm的Fe3O4或γ-Fe2O3；
2)在磁性颗粒表面通过溶胶-凝胶过程包覆水合二氧化钛沉淀：将酸，醇和水的混合溶液加入到步骤1)中的磁性颗粒分散液中进行溶胶-凝胶反应，反应结束后进行固液分离获得磁性固体，制得所述Low-K材料金属去除剂；其中，所述的酸选自盐酸、硝酸、磷酸或者硫酸中的一种或几种；所述溶胶-凝胶过程的反应温度为20～70℃；所述Low-K材料金属去除剂中水合二氧化钛质量含量为30～70％；
上述步骤中，所述磁性颗粒的质量和所述钛酸丁酯的体积比为1：0.5～1：15；所述钛酸丁酯和所述醇的体积比为1：2～1：30，其中所述醇的体积是指制备有机液态源Low-K材料金属去除剂的方法的步骤1)和步骤2)中所使用的总的醇体积；所述钛酸丁酯与所述酸的体积比为1：0.005～1：0.5；所述钛酸丁酯和水的体积比为1：0.1～1：2.0。
优选地，所述磁性颗粒的质量和所述钛酸丁酯的体积比为1：2～1：l0。
优选地，所述钛酸丁酯和所述醇的体积比为1：3～1：20。
优选地，所述钛酸丁酯与所述酸的体积比为1：0.02～1：0.3。
优选地，所述钛酸丁酯和水的体积比为1：0.2～1：1.0。
上述步骤2)中溶胶-凝胶反应的时间以溶液完全凝胶化为准。
其中步骤2)中的水为钛酸丁酯的水解的反应物，通过控制加入酸，醇和水的混合溶液的浓度和流速，使得钛酸丁酯在溶液中在磁性颗粒的表面形成凝胶化。
上述步骤中所述的醇选自现有技术中常用醇类，包括甲醇、乙醇、丙醇或丁醇中的一种或几种。
为了让溶胶凝胶反应更好的进行，也可以对磁性颗粒进行交联处理。
优选地，在步骤1)中，对所述磁性颗粒预先进行表面交联处理，所述交联处理的步骤为：将交联剂加入所述磁性颗粒的水溶液中进行交联处理，所述磁性颗粒与所述交联剂的质量比1：0.1～3.0。交联处理完成后通过固液分离获得交联处理后的磁性颗粒。
或者，优选地，将交联剂加入上述步骤2)所述酸，醇和水的混合溶液中对所述磁性颗粒进行交联处理，所述磁性颗粒与所述交联剂的质量比1：0.1～3.0。交联处理步骤与溶胶-凝胶反应同时进行。
优选地，所述的交联剂选自戊二醛或者硅烷偶联剂中的一种或两种。
更优选地，所述的硅烷偶联剂选自KH570、KH560或KH550中的一种或几种。
优选地，上述交联处理步骤中，在搅拌条件下，将交联剂加入所述磁性颗粒的水溶液中。
优选地，上述交联处理步骤中，在室温至90℃的温度条件下，将交联剂加入所述磁性颗粒的水溶液中。
更优选地，上述交联处理步骤中，在50～80℃的温度条件下，将交联剂加入所述磁性颗粒的水溶液中。
或者，优选地，上述步骤1)中的所述磁性颗粒在使用前先用无水醇溶液浸泡搅拌处理，然后进行固液分离、并对固液分离出来的磁性颗粒进行干燥处理。所述的无水醇溶液为现有技术中常用的醇类，包括甲醇、乙醇或丙醇。
优选地，所述制备有机液态源Low-K材料金属去除剂的方法还包括对步骤2)中磁性固体在60～120℃条件下进行陈化处理。
本发明中所述的陈化处理为：在步骤2)中反应结束后，所述磁性固体再放置在60～120℃条件下以及不搅拌继续反应。陈化处理的时间为至少12小时。陈化处理时在不搅拌的条件下反应，不同于溶胶-凝胶反应需要在搅拌条件下进行。
所述的制备Low-K材料金属去除剂的方法还包括对陈化处理后的磁性固体进行多次水洗和固液分离，除去未反应的杂质以及未包覆磁性颗粒的水合二氧化钛，最后使用pH为2.0～6.0蒸馏水进行洗涤、固液分离后对磁性固体进行干燥处理。
本发明还公开了所述的有机液态源Low-K材料金属去除剂在去除有机液态源中金属杂质的应用。
优选地，所述的Low-K材料金属去除剂去除有机液态源中金属杂质的过 程包括如下步骤：
步骤1，将有机液态源和所述Low-K材料金属去除剂搅拌均匀形成混合物；
步骤2，将前述有机液态源和Low-K材料金属去除剂的混合物加热汽化，然后冷凝收集不同阶段的馏分。
优选地，所述有机液态源和所述Low-K材料金属去除剂的质量比为10000：1～10：1。
优选地，所述有机液态源和Low-K材料金属去除剂在精馏釜中形成混合物，在精馏塔中汽化、冷凝。
与现有技术相比，本发明的有益效果如下：
1、所述的Low-K材料金属去除剂制备方法简单：采用温和的溶胶-凝胶反应制备；原料成本低廉、降低了生产成本；通过外加磁场即可实现固液分离，固液分离的速度快、能耗低。
2、所述Low-K材料金属去除剂能够有效去除有机液态源中的微量金属杂质。在精馏塔中将有机液态源和Low-K材料金属去除剂混合，通过精馏方式进行提纯，使得有机液态源的纯度达到99.9％以上。
附图说明
图1是本发明实施例中Low-K材料金属去除剂去除有机液态源中金属杂质所使用的精馏设备的结构示意图。
具体实施方式
实施例1
称取40mL钛酸丁酯、400mL无水乙醇，和4g的Fe3O4放入三口烧瓶，超声分散10～30分钟，然后将三口烧瓶移入50℃水浴中搅拌10～60分钟。另外量取10mL的H2O，150mL无水乙醇，1.2mL浓盐酸配制成溶液，由恒压滴液漏斗将该溶液缓慢加入上述三口烧瓶中，反应6h后停止。产物自然冷却到室温，用磁分离的方法分离得到磁性复合水合二氧化钛颗粒，再将磁性复合水合二氧化钛颗粒移入80℃烘箱中继续陈化 24h，得金属去除剂A。
经X荧光元素分析和TGA水含量分析，金属去除剂A中水合二氧化钛含量(重量含量)占46％。
实施例2
(1)称取10g Fe3O4和300mL水放入三口烧瓶，超声分散10～30分钟，然后将三口烧瓶移入80℃水浴中搅拌10～60分钟，另外量取10mL25％的戊二醛水溶液和50mL水配置成溶液，由恒压滴液漏斗将该溶液缓慢加入上述三口烧瓶中，反应6h后停止。产物自然冷却到室温，用磁分离的方法分离得到戊二醛改性Fe3O4颗粒烘干后待用。
(2)称取40mL钛酸丁酯、400mL无水乙醇，和4g的第(1)步获得的Fe3O4放入三口烧瓶，超声分散10～30分钟，然后将三口烧瓶移入50℃水浴中搅拌10～60分钟。另外量取10mL的H2O，150mL无水乙醇，1.2mL浓盐酸配制成溶液，由恒压滴液漏斗将该溶液缓慢加入上述三口烧瓶中，反应6h后停止。产物自然冷却到室温，用磁分离的方法分离得到磁性复合水合二氧化钛颗粒。磁性颗粒移入80℃烘箱中继续陈化24h，得金属去除剂B。
经X荧光元素分析和TGA水含量分析，金属去除剂B中水合二氧化钛含量(重量含量)占53％。
实施例3
称取1000mL钛酸丁酯、4000mL无水乙醇，和150g的Fe3O4放入三口烧瓶，超声分散10～30分钟，然后将三口烧瓶移入50℃水浴中搅拌10～60分钟。另外量取700mL的H2O，500mL无水乙醇，20mL浓盐酸配制成溶液，由恒压滴液漏斗将该溶液缓慢加入上述三口烧瓶中，反应6h后停止。产物自然冷却到室温，用磁分离的方法分离得到磁性复合水合二氧化钛颗粒，再将磁性复合水合二氧化钛颗粒移入80℃烘箱中继续陈化24h，得金属去除剂C。
经X荧光元素分析和TGA水含量分析，金属去除剂C中水合二氧化钛含量(重量含量)占63％。
实施例4
称取1300mL钛酸丁酯、4000mL无水乙醇，和650g的Fe3O4放入三口烧瓶，超声分散10～30分钟，然后将三口烧瓶移入50℃水浴中搅拌10～60分钟。另外量取800mL的H2O，500mL无水乙醇，200mL25％戊二醛溶液，25mL浓盐酸配制成溶液，由恒压滴液漏斗将该溶液缓慢加入上述三口烧瓶中，反应6h后停止。产物自然冷却到室温，用磁分离的方法分离得到磁性复合水合二氧化钛颗粒，再将磁性复合水合二氧化钛颗粒移入80℃烘箱中继续陈化24h，得金属去除剂D。
经X荧光元素分析和TGA水含量分析，金属去除剂D中水合二氧化钛含量(重量含量)占47％。
实施例5
上述实施例中制备的金属去除剂去除有机液态源中的微量金属杂质时，可在精馏塔中进行。参见图1，该图为Low-K材料金属去除剂去除有机液态源中金属杂质所使用的精馏设备的结构示意图。如图1所示，所述精馏设备包括：磁力加热搅拌器11、精馏釜12、精馏柱13和冷凝器14。
所述磁力加热搅拌器11与精馏釜12配合，适于将精馏釜12中的被精馏材料进行搅拌和加热。所述精馏釜12，其材料为石英或不锈钢，开口可以有两个、三个或四个，大小为5L～20L。
所述精馏柱13位于所述精馏釜12的开口上方，其材质为石英或不锈钢，内径为30mm～80mm，柱高1.2m～2m，填料的填充高度为1.2m～2m，可以是不锈钢θ环填料、不锈钢三角螺旋填料，石英θ环填料等。
所述冷凝器14位于所述精馏柱13上方，其中冷凝液由进口b进入，从出口c出去。所述冷凝器的顶部开口v适于连接真空机台，适于被抽真空。
所述接收瓶15、16、17与精馏柱13连接，适于分别接收不同沸点的馏分。
阀门18、19、110连接在接收瓶15、16、17和精馏柱13之间，主要为控制不同馏分流入不同接收瓶。
利用上述精馏设备对有机液态源进行提纯的过程如下：
有机液态源原料为工业级三氟丙基环三硅氧烷(纯度为98.5％)，主要有机硅杂质为高沸点有机硅氧烷等，金属离子总含量为6.2ppm。
将2500g工业级三氟丙基环三硅氧烷和8g金属去除剂C加入到精馏釜12中，在常压下将磁力加热搅拌器11的温度升到40℃、搅拌3h。抽真空至真空度为4.5KPa，将磁力搅拌加热器温度升到150℃，将塔顶60～136℃馏分收集在接收瓶15中。无馏分流出后，将磁力加热搅拌器温度升高至160℃，将塔顶136～137℃馏分收集在接收瓶16中。待塔顶馏分温度稳定在137℃后，将塔顶137℃馏分收集在接收瓶17中。取样分析，通过GC和ICP-MS测试结果可知，接收瓶17中三氟丙基环三硅氧烷纯度为99.98％，金属含量如表1所示(单位：ppb)。
表1，三氟丙基环三硅氧烷提纯后的金属含量
元素 K Ca Na Mg Fe
含量 <1 <1 <1 <1 <1
实施例6
有机液态源原料为工业级八甲基环四硅氧烷(纯度98.0％)，主要有机硅杂质为六甲基环三硅氧烷，金属离子总含量为8.5ppm。
将3000g工业级八甲基环四硅氧烷和5g金属去除剂B加入到精馏釜12中，在25℃和常压下搅拌3h。抽真空至真空度为20KPa，将磁力搅拌加热器温度升到140℃，将塔顶80～105℃馏分收集在接收瓶15中。无馏分流出后，将磁力搅拌加热器温度升高至150℃，将塔顶105～106℃馏分收集在接收瓶16中。待塔顶馏分温度稳定在106℃后，将塔顶106℃馏分收集在接收瓶17中。取样分析，通过ICP-MS测试结果可知，接收瓶17中八甲基环四硅氧烷纯度99.96％，金属含量如表2所示(单位：ppb)。
表2，八甲基环四硅氧烷提纯后的金属含量
元素 Na Mg K Ca Fe Co Ni Cu
含量 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1
元素 Zn Ga Mo Ag Cd Sn Ba Pt
含量 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1
元素 Au Tl Pb As Ti V W Nb
含量 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1
元素 Zr Ta Bi Be Ge Sr Sb  
含量 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1  
实施例7
有机液态源原料为工业级三氟丙基环三硅氧烷(纯度为98.5％)，主要有机硅杂质为高沸点有机硅氧烷等，金属离子总含量为6.2ppm。
将2500g工业级三氟丙基环三硅氧烷和8g金属去除剂C加入到精馏釜12中，在常压下将磁力加热搅拌器11的温度升到40℃、搅拌3h。抽真空至真空度为4.5KPa，将磁力搅拌加热器温度升到150℃，将塔顶60～136℃馏分收集在接收瓶15中。无馏分流出后，将磁力加热搅拌器温度升高至160℃，将塔顶136～137℃馏分收集在接收瓶16中。待塔顶馏分温度稳定在137℃后，将塔顶137℃馏分收集在接收瓶17中。取样分析，通过GC和ICP-MS测试结果可知，接收瓶17中三氟丙基环三硅氧烷纯度为99.96％，金属含量如表3所示(单位：ppb)。
表3，三氟丙基环三硅氧烷提纯后的金属含量
元素 K Ca Na Mg Fe
含量 <1 <1 <1 <1 <1
实施例8
有机液态源原料为工业级八甲基环四硅氧烷(纯度98.0％)，主要有机硅杂质为六甲基环三硅氧烷，金属离子总含量为8.5ppm。
将3000g工业级八甲基环四硅氧烷和5g金属去除剂D加入到精馏釜12中，在25℃和常压下搅拌3h。抽真空至真空度为20KPa，将磁力搅拌加热器温度升到140℃，将塔顶80～105℃馏分收集在接收瓶15中。无馏分流出后，将磁力搅拌加热器温度升高至150℃，将塔顶105～106℃馏分收集在接收瓶16中。待塔顶馏分温度稳定在106℃后，将塔顶106℃馏分收集在接收瓶17中。取样分析，通过ICP-MS测试结果可知，接收瓶17中八甲基环四硅氧烷纯度99.95％，金属含量如表4所示(单位： ppb)。
表4，八甲基环四硅氧烷提纯后的金属含量
元素 K Ca Na Mg Fe
含量 <1 <1 <1 <1 <1
上述仅为本发明的部分优选实施例，本发明并不仅限于实施例的内容。对于本领域中的技术人员来说，在本发明技术方案的构思范围内可以有各种变化和更改，所作的任何变化和更改，均在本发明保护范围之内。

Claims (10)

  1. 一种有机液态源Low-K材料金属去除剂，其特征在于：所述有机液态源Low-K材料金属去除剂为磁性复合水合二氧化钛，所述磁性复合水合二氧化钛的内核物质为粒径10nm～30μm的Fe3O4或γ-Fe2O3磁性颗粒，在所述磁性颗粒的表面包覆有水合二氧化钛，所述磁性颗粒与所述水合二氧化钛为共价键连接，其中，所述磁性复合水合二氧化钛中水合二氧化钛质量含量为30～70％。
  2. 一种制备有机液态源Low-K材料金属去除剂的方法，包括如下步骤：
    1)磁性颗粒分散液的制备：将磁性颗粒加入到钛酸丁酯的醇溶液中制成磁性颗粒分散液；所述的磁性颗粒为粒径为10nm～30μm的Fe3O4或γ-Fe2O3；
    2)在磁性颗粒表面通过溶胶-凝胶过程包覆水合二氧化钛沉淀：将酸，醇和水的混合溶液加入到步骤1)中的磁性颗粒分散液中进行溶胶-凝胶反应，反应结束后进行固液分离获得磁性固体，制得所述Low-K材料金属去除剂；其中，所述的酸选自盐酸、硝酸、磷酸或者硫酸中的一种或几种；所述溶胶-凝胶过程的反应温度为20～70℃；所述Low-K材料金属去除剂中水合二氧化钛质量含量为30～70％；
    上述步骤中，所述磁性颗粒的质量和所述钛酸丁酯的体积比为1：0.5～1：15；所述钛酸丁酯和所述醇的体积比为1：2～1：30，其中所述醇的体积是指制备有机液态源Low-K材料金属去除剂的方法的步骤1)和步骤2)中所使用的总的醇体积；所述钛酸丁酯与所述酸的体积比为1：0.005～1：0.5；所述钛酸丁酯和水的体积比为1：0.1～1：2.0。
  3. 如权利要求2所述的方法，其特征在于：在步骤1)中，对所述磁性颗粒预先进行表面交联处理，所述交联处理的步骤为：将交联剂加入所述磁性颗粒的水溶液中进行交联处理，所述磁性颗粒与所述交联剂的质量比1：0.1～3.0。
  4. 如权利要求2所述的方法，其特征在于：在步骤2)中，将交联剂加入上述步骤2)所述酸，醇和水的混合溶液中对所述磁性颗粒进行交联处理，所述磁性颗粒与所述交联剂的质量比1：0.1～3.0。
  5. 如权利要求2所述的方法，其特征在于：所述方法还包括对步骤2) 中磁性固体在60～120℃条件下进行陈化处理。
  6. 如权利要求5所述的方法，其特征在于：所述的制备Low-K材料金属去除剂的方法还包括对陈化处理后的磁性固体进行多次水洗和固液分离，除去未反应的杂质以及未包覆磁性颗粒的水合二氧化钛，最后使用pH为2.0～6.0蒸馏水进行洗涤、固液分离后对磁性固体进行干燥处理。
  7. 权利要求1所述的有机液态源Low-K材料金属去除剂在去除有机液态源中金属杂质的应用。
  8. 如权利要求7所述的有机液态源Low-K材料金属去除剂在去除有机液态源中金属杂质的应用，其特征在于，所述金属去除剂去除有机液态源中金属杂质的过程包括如下步骤：
    步骤1，将有机液态源和所述Low-K材料金属去除剂搅拌均匀形成混合物；
    步骤2，将前述有机液态源和Low-K材料金属去除剂的混合物加热汽化，然后冷凝收集不同阶段的馏分。
  9. 如权利要求8所述的有机液态源Low-K材料金属去除剂在去除有机液态源中金属杂质的应用，其特征在于：所述有机液态源和所述Low-K材料金属去除剂的质量比为10000：1～10：1。
  10. 如权利要求8所述的有机液态源Low-K材料金属去除剂在去除有机液态源中金属杂质的应用，其特征在于：所述有机液态源和Low-K材料金属去除剂在精馏釜中形成混合物，在精馏塔中汽化、冷凝。
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113583038A (zh) * 2021-07-27 2021-11-02 合盛硅业(鄯善)有限公司 八甲基环四硅氧烷提纯方法
CN114751929A (zh) * 2022-05-18 2022-07-15 江苏南大光电材料股份有限公司 半导体级二乙基乙氧基铝的制备方法

Families Citing this family (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108097216A (zh) * 2017-12-06 2018-06-01 金昱轩 一种环保吸附磁性微球及其制备方法
CN108380178A (zh) * 2018-03-12 2018-08-10 秋晓东 一种生态修复剂的制备方法及其对放射性核素的吸附工艺
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CN113466003B (zh) * 2021-06-21 2022-06-28 无锡恩捷新材料科技有限公司 一种测试超高分子量聚乙烯内含金属异物的样品的制样方法及其制样装置
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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5777145A (en) * 1997-09-19 1998-07-07 Dow Corning Corporation Removal of chlorocarbons from organochlorosilanes
CN102319564A (zh) * 2011-06-15 2012-01-18 北京科技大学 一种双层空腔结构及海胆状的二氧化钛磁性微球制备方法
CN102614818A (zh) * 2012-03-27 2012-08-01 复旦大学 一种磁性介孔二氧化钛核壳式复合微球及其制备方法和应用
CN103145752A (zh) * 2013-03-20 2013-06-12 上海中科高等研究院 去除有机硅中金属离子的方法
CN103896980A (zh) * 2014-04-23 2014-07-02 中国科学院上海高等研究院 有机硅化合物的提纯方法

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5777145A (en) * 1997-09-19 1998-07-07 Dow Corning Corporation Removal of chlorocarbons from organochlorosilanes
CN102319564A (zh) * 2011-06-15 2012-01-18 北京科技大学 一种双层空腔结构及海胆状的二氧化钛磁性微球制备方法
CN102614818A (zh) * 2012-03-27 2012-08-01 复旦大学 一种磁性介孔二氧化钛核壳式复合微球及其制备方法和应用
CN103145752A (zh) * 2013-03-20 2013-06-12 上海中科高等研究院 去除有机硅中金属离子的方法
CN103896980A (zh) * 2014-04-23 2014-07-02 中国科学院上海高等研究院 有机硅化合物的提纯方法

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113583038A (zh) * 2021-07-27 2021-11-02 合盛硅业(鄯善)有限公司 八甲基环四硅氧烷提纯方法
CN114751929A (zh) * 2022-05-18 2022-07-15 江苏南大光电材料股份有限公司 半导体级二乙基乙氧基铝的制备方法

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